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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
1

Kinetic Modeling of the Adsorption of Mercury Chloride Vapor on Spherical Activated Carbon by Thermogravimetric Anaylysis

CHEN, WEI-CHIN 25 August 2004 (has links)
This study investigated the adsorptive capacity and isotherm of HgCl2 onto spherical activated carbons (SAC) via thermogravimetric analysis (TGA). Activated carbon injection (ACI) is thought as the best available control technology (BACT) for mercury removal from flue gas. There are two major forms of vapor-phase mercury, Hgo and Hg2+, of which HgCl2 accounts for 60-95% of total mercury. Mercury emitted from the incineration of municipal solid wastes (MSW) could cause severely adverse effects on human health and ecosystem since it exists mainly in vapor phase due to high vapor pressure. Although the adsorptive capacity of HgCl2 onto activated carbon has been studied in previous adsorption column tests, only a few studies have thoroughly investigated the adsorption isotherms of HgCl2 onto SAC. Equilibrium and kinetic studies are important towards obtaining a better understanding of mercury adsorption. Many investigations have addressed the relationship between sorption kinetics and equilibrium for different adsorbent/adsorbate combinations. For the removal of vapor-phase mercury, several bench-pilot, and full-scale tests have be proceeded to examine the influence of carbon types, carbon structures, carbon surface characteristics, injection methods (dry or wet), amount of carbon injected, and flue gas temperature on mercury removal. In addition, the dynamics of spherical activated carbons (SAC) adsorbers for the uptake of gas-phase mercury was evaluated as a function of temperature, influent concentration of mercury, and empty-bed residence time. However, only a few studies investigated the adsorption isotherms of HgCl2 onto activated carbons. In this study, TGA was applied to obtain the adsorptive capacity of HgCl2 onto SAC with adsorption temperature (30~150oC) and influent HgCl2 concentration (50~1,000£gg/m3). Experimental results indicated that the adsorptive capacity of HgCl2 onto SAC was 0.67and 0.20 mg/gC at 30¡B70 and 150oC, respectively. This study investigated the adsorptive capacity of HgCl2 vapor onto SAC via TGA analysis. Experimental results indicated that the adsorptive capacity of SAC decreased with the increase of the adsorption temperature. Furthermore, the results suggested that that the adsorption of SAC on HgCl2 vapor was favorable equilibrium at 30 and 70¢J and unfavorable equilibrium at 150¢J. In comparison of the experimental data with isotherm equations, Freundlich isotherm fitted the experimental results better than Langmuir isotherm. The model simulations were found to fit very well to the high concentration experimental kinetic data for both adsorption and desorptionusing two adjust parameter, effective diffusivity, and the Freundlich isothermexponent.¡@The extracted model parameter, effective diffusivity and n, were then used to predict the experimental kinetic data for the same combination at other concentrations.
2

Adsorption and Desorption of Mercury Chloride on Sulfur-impregnated Activated Carbon by Thermogravimetric Analysis (TGA)

Syue, Sheng-Han 27 August 2008 (has links)
This study investigated the adsorptive and desorption capacity of HgCl2 onto powdered activated carbon derived from carbon black of pyrolyzed waste tires (CPBAC) via thermogravimetric analysis (TGA). Due to incomplete classification and recycling of municipal solid wastes (MSW), they still mix with a lot of hazardous materials, which unfortunately can not be removed by incinerators and air pollution control devices(APCDs). Among them, mercury and its pollutants attract more attention by people. Mercury and its pollutants emitted from the incineration of municipal solid wastes could cause severely adverse effects on human health and ecosystem since they exist mainly in vapor phase due to high vapor pressure. If they can not be remove by the air pollution control devices, they will be emitted to the atmosphere and cause serious effects on environmental ecology via various routes. Activated carbon has been widely applied to the treatment of organic compounds and heavy metals in wastewater and waste gas stream. However, the adsorptive capacity of activated carbon decreases with adsorption temperature. The low adsorptive capacity of activated carbon at high temperature (>150 oC) can be overcome by impregnated activated carbons. Previous study reported that sulfur impregnated powdered activated carbons could effectively remove the vapor-phase elemental mercury (Hgo) emitted from MSW incinerators and utility power plants. However, the impregnated typically used is sulfur (S) which is solely applied for the adsorption of elemental mercury (Hgo). Besides, these studies seldom investigate the distribution of impregnated sulfur in the inner pores of activated carbon and its effects on the specific surface area and pore size distribution. Thus, this study was to investigate the fundamental mechanisms for the adsorption/desorption of HgCl2 by/from sulfur impregnated PAC. Experimental results indicated that the sulfur content of sulfur impregnated CBPAC decreased with increasing impregnation temperatures form 400 to 650 oC; while the surface area of sulfur impregnated CBPAC increased with impregnation temperatures. In this study, TGA was applied to obtain the adsorptive capacity of HgCl2 onto CBPAC with adsorption temperature (150oC) and influent HgCl2 concentration (100~500 £gg/m3). Experimental results indicated that the adsorptive capacity of CBPAC increased with the increase of influent HgCl2 concentration and surface area of the activated carbon. This study revealed that the impregnation of sulfur on CBPAC could increase its adsorption capacity at high temperatures. Desorption experimental parameters included desorption temperature (400, 500, and 600 oC), heating rate (10, 15, and 20 oC /min) and regeneration cycle (1~7 cycles). In probing into the regeneration efficiency of CBPAC, experiments were conducted at the desorption times of 60 and 30 min. The results suggested the regeneration efficiency of carbon under 30 min was generally highter than that under 60 min. Because the desorption time was more longer and the sulfur content was lesser. Therefore, the regeneration times was reduce. Experimental results indicated that the mechanism of HgCl2 desorption from the spent CPBAC was strongly affected by desorption temperature. Both the desorption efficiency and the desorption rate of HgCl2 increased dramatically with desorption temperature. The desorption heat of HgCl2 (823 KJ/mole) was much higher than the vaporization heat of HgCl2 (59.2 KJ/mole), indicating that the adsorption of HgCl2 on sulfur impregnated CBPAC was chemical adsorption. Consequently, raising desorption temperature could enhance the desorption of HgCl2 and shorten the duration for HgCl2 desorption. Moreover, the formation of HgS during the desorption of HgCl2 from activated carbons can be proved by the surface characteristics of sulfur impregnated activated carbons. Results obtained from the regeneration of sulfur impregnated activated carbons indicated that the regeneration cycles decreased as the desorption duration increased. It was attributed to the potential desorption of sulfur from actived carbons, which thus decreased the adsorptive capacity and the regeneration cycles.
3

Application of Thermogravimetric Analysis (TGA) Technique on Adsorption Capacity and Adsorption and Desorption Kinetics of Sulfur-impregenated Activated Carbon Saturated with Gaseous Mercury Chloride

Chen, Wei-chin 09 July 2010 (has links)
The objective of this study is to investigate the influence of sulfur compounds (S and Na2S) for powdered activated carbon derived from carbon black of pyrolyzed waste tires (CPBAC). Besides, this study investigated the distribution of impregnated sulfur in the inner pores of activated carbon and its effected on the specific surface area and pore size distribution. This study investigated the fundamental mechanisms by analysis of thermodynamic properties and to establish the kinetic models for the adsorption/desorption of HgCl2 by/from sulfur impregnated CBPAC. Furthermore, this study investigated the adsorptive and desorption capacity of HgCl2 onto CPBAC via thermogravimetric analysis (TGA). Experimental results indicated that the specific surface area of sulfur impregnated CBPAC with elemental S (S0) was larger than sulfur impregnated CBPAC with Na2S. Besides, the sulfur content of sulfur impregnated CBPAC increased with increasing the surface area of CBPAC under the same impregnated temperature. And, the adsorptive capacity of CBPAC increased with the increase of influent HgCl2 concentration and surface area of the activated carbon. According to the experimental results of the adsorption capacity under the differential sulfur content, its indicated that the affection of sulfur content for adsorption capacity of HgCl2 was much than HgCl2 concentration and surface area of the activated carbon. The desorption energys were 266 and 282 kJ/mole for HgCl2 desorption from saturated CBPAC-S0 and CBPAC-Na2S, respectively. The results showed the process of HgCl2 adsorption onto CBPAC was in favor of a physisorbed state of HgCl2 at the adsorption temperature of 150 oC but the process of HgCl2 adsorption onto CBPAC which impregated was in favor of a chemisorbed state of HgCl2 at the adsorption of 150 oC. The value of ∆G for CBPAC at the adsorption temperature of 30 ~150 oC were ranged from -15.28 kJ/mole to -26.63 kJ/mole. The value of ∆G for CBPAC-S0 at the adsorption temperature of 30~150 oC ranged from -23.45 kJ/mole to -32.09 kJ/mole. The value of ∆G for CBPAC-Na2S at the adsorption temperature of 30~150 oC ranged from -22.84 kJ/mole to -32.72 kJ/mole. The results showed negative values of ∆G confirmed the feasibility of adsorption process and the spontaneous nature for the adsorption of HgCl2. The value of ∆H for CBPAC at the adsorption temperature of 30 ~150 oC ranged from -35.58 kJ/mole to -35.82 kJ/mole. The value of ∆H for CBPAC-S0 at the adsorption temperature of 30 ~150 oC ranged from -38.07 kJ/mole to -52.49 kJ/mole. The value of ∆H for CBPAC-Na2S at the adsorption temperature of 30~150 oC was -37.45 kJ/mole to -53.12 kJ/mole. A negative ∆H suggested that the adsorption of HgCl2 is an exothermic process. Besides, the adsorptive behavior of HgCl2 for two activated carbons (CBPAC-Na2S and CBPAC-S0) at high temperature (110 ¢J and 150 ¢J ) was the same chemical reaction mechanism due to the same ∆H. Besides, the results of model simulation indicated that modified adsorption kinetic model based on pore diffusion scheme developed in this study could successfully simulate the transport and adsorption of HgCl2 by considering the chemical reaction within the inner pores of carbon grains at 150 oC.

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